4 - alkyl and cyclohexyl alkyl dicyclohexyl peroxydicarbonates



United States Patent Office Patented Mar. 10, 1970 4 ALKYL ANDCYCLOHEXYL ALKYL DICYCLOHEXYL PEROXYDICARBONATES Hans GfGerritsen,Deventer, Hendrik Hansma,

Schalkhaar, and Hans Jaspers, Deventer, Netherlands, assignors toKouinklijke Industrieele Maatschappij Noury & van der Lande N.V.,Deventer, Netherlands, a corporation of the Netherlands No Drawing.Filed Feb. 17, 1967, Ser. No. 616,775

Claims priority, application Great Britain, Feb. 28, 1966,

6 Int. Cl. C07c 73 /00, 69/00; C08f 1/60 US. Cl. 260453 6 ClaimsABSTRACT OF THE DISCLOSURE The present invention relates to4-substituted dicyclohexylperoxydicarbonates capable of use, forexample, in the polymerization of polymerizable unsaturated monomers;the invention also relates to a process for preparingthe 4-substituteddicyclohexylperoxydicarbonates and to polymerizable compositionsconsisting essentially of a polymerizable monomer and a 4-substituteddicyclohexylperoxydicarbonate. The 4-suhstituent is a cyclohexyl radicalor an alkyl radical or a cyclohexylalkyl radical, said alkyl orcyclohexylalkyl radical having up to 10 carbon atoms.

BACKGROUND OF THE INVENTION Field of the invention The present inventionlies in the field of novel organic peroxidic compounds, methods fortheir synthesis, their use in the peroxidic polymerization ofpolymerizable unsaturated monomers, and the corresponding polymerizablecompositions.

Description of the prior art at slightly higher temperatures, decomposeexplosively.

Due to this undesirable characteristic, these prior artperoxydicarbonates may only be handled, transported and stored underrefrigeration.

SUMMARY OF THE INVENTION Surprisingly, it has now been found thatpreviously unknown 4-substituted dicyclohexylperoxydicarbonates havingthe structural formula in which R represents a cyclohexyl radical or analkyl radical or a cyclohexylalkyl radical, said alkyl orcyclohexylalkyl radicals having up to 10 carbon atoms, are stable atroom temperature so that they need not be refrigerated or otherwisestabilized during transport and/or storage.

The novel 4-substituted dicyclohexylperoxydicarbonates are solid at roomtemperature and they may be used as oxidizing agents in bleaching flour,as driers for linseed, tung, soyabean and other oils, as initiators inthe polymerization of polymerizable unsaturated monomers containingvinyl groups, such as vinyl chloride, vinylidene chloride, vinylbromide, acrylamide, N-substituted methacrylamides, acrylonitrile, vinylacetate, methylmethacrylate or compounds containing allyl groups such asallyl acetate, diethyleneglycol-bis (allylcarbonate) and otherpolymerizable compounds, such as ethylene.

As initiators in the polymerization of vinyl chloride, the 4-substituteddicyclohexylperoxydicarbonates are more effective in equivalent molaramounts than the peroxydicarbonates hitherto employed which isadvantageous from an economical point of view. 4-substituteddicyclohexylperoxydicarbonates preferably used in accordance with thepresent invention are bis(4-isopropylcyclohexyl)peroxydicarbonate,bis(4-tertiarybutylcyclohexyl)peroxydicarbonate, bis(4-tertiaryamyl-cyclohexyl) peroxydicarbonate,bis(4-cyclohexylisopropylcyclohexyl)peroxydicarbonate,bis(4-cyclohexylcyclohexyl)peroxydicarbonate.

The 4-substituted dicyclohexylperoxydicarbonates according to thepresent invention may be prepared by reacting the correspondinghaloformates, preferably the chloroformates, with an aqueous alkalinehydrogen peroxide solution, preferably an aqueous sodiumhydroxidehydrogen peroxide solution, at a temperature below 45 C. andisolating the peroxydicarbonates thus formed.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order still better toillustrate the nature of the present invention the following detailedexamples are set forth, it being understood, however, that thisdescription and these examples are presented here by way of illustrationonly and not as limiting the scope of the invention.

EXAMPLE 1 109.2 g. of an aqueous 33% w./w. NaOH solution were added withstirring to 36.7 g. of aqueous 50% w./w. H 0 solution and 675 ml. ofwater. The temperature of the mixture was then adjusted to 40 C.Subsequently 0.69 ml. of an aqueous 27% W./w. sodium(7-ethyl-2-methylundecyl-4)sulphate (trademark Tergitol An4) were addedas an emulsifier.

208.1 g. of 94.5% 4-tertiarybutylcyclohexylchloroformate were addeddropwise with continuous stirring at 40 C. for 45 minutes andsubsequently 7.4 g. of an aqueous 50% w./w. H O -solution, whereuponstirring was continued for 45 minutes at 40 C. After cooling thereaction mixture to room temperature, the peroxydicarbonate formed wasfiltered off at 30 0., dried and recrystallized from pentane. 196 g. ofhis(4-tertiarybutylcyclohexyl) peroxydicarbonate were obtained, yield92% (calculated on the 4-tertiarybutylcyclohexylchloroformate charged).

EXAMPLE 2 In the same way as described in Example 1,bis(4-tertiaryamylcyclohexyl)peroxydicarbonate was prepared startingfrom 4-tertiaryamylcyclohexylchloroforrnate.

EXAMPLE 3 In the same way as described in Example 1,bis(4-isopropylcyclohexyl)peroxydicarbonate was prepared starting from4-isopropylcyclohexylchloroformate.

EXAMPLE 4 3 EXAMPLE In the same way as described in Example 1,bis(4-cyclohexylcyclohexyl)peroxydicarbonate was prepared starting 4EXAMPLE 7 The following composition was used in the suspensionpolymerizationof vinyl chloride:

from 4-cyclohexylcyclohexylchloroformate. Parts Data relating to theseveral peroxydicarbonates thus 5 Vinyl chloride 100 prepared accordingto the respective Examples 15 ar Distilled water 300 as follows: Elvanol5042 (a polyvinyl alcohol) 0.3

Example Det. Calc. Det. Cale. Det. Cale. Det. Cale. Det. Cale.

Percent:

Act. 0 4.00 4. 03 3. 71 3. 75 4.23 4.32 2. 90 2.99 3.43 3. 55 66v 2667.75 67. 60 64v 13 64. 95 72. 27 71. 90 69. 55 69. 30 9. 62 10. 02 9.93 9. 42 9. 10.46 10.17 9. 63 9. 39 99.6 98.0 EXAMPLE 6Peroxydicarbonate, various amounts, as indicated below.

In order to determine their stability, samples both ofperoxydicarbonates according to the present invention and of knownperoxydicarbonates were placed in a Pyrex glass tube and kept at aconstant temperature of C. using a constant temperature bath.

The rate of decomposition of the peroxydicarbonates was measured bydetermining the active oxygen content of the samples at given timeintervals. The data obtained are tabulated hereafter:

Stability at 30 C.

Z being:

CH Complete decomposition within 0.5 hour.

CH CH3 n-C H Complete decomposition within 2 days.

CH3 Do.

s CH CH3 (3H3 No decomposition after 2 months. CH (|3 S ([3113 D0. CH5(|1 S (3H D0. S (J S No. 1 =diisopropylperoxydicarbonate.

No. 2 dieyclohexylperoxydiearbonate.

No. 3 bis (4-tertiarybutylcyclohexyl) peroxydlcarb onate. N o. 4 bis(4-tertiaryamyl-cyelohexyl) peroxydicarb on ate.

From the foregoing table it can readily be seen that withbis(4-tertiarybutylcyclohexyl)peroxydicarbonate or withbis(4-tertiaryamylcyclohexyl)peroxydicarbonate employed in the samemolar ratio and in the same time, a higher conversion is obtained thanwith diisopropylperoxydicarbonate or with dicyclohexylperoxydicarbonate;or alternatively, the same conversion is achieved within a shorter time.

What is claimed is:

1. An organic peroxydicarbonate having the general formula in which Rrepresents a cyclohexyl radical or an alkyl or cyclohexylalkyl radical,said alkyl or cyclohexylalkyl radicals having from 3 to 10 carbon atoms,and being bound to the nucleus through a secondary or tertiary carbonatom.

2. A compound as defined in claim 1, wherein the organicperoxydicarbonate is bis(4-isopropylcyclohexyl) peroxydicarbonate.

organic peroxydicarbonate isbis(4-cyclohexylcyc1oheXyDperoxydicarbonate.

References Cited UNITED STATES PATENTS 2,370,588 2/1945 Strain 260-453 62,517,964 8/1950 Bissinger 260-453 3,108,093 10/1963 Pajaczkowski et a1.260'453 X 3,377,373 4/1968 Lederer et a1 260-463 OTHER REFERENCES Strainet al., Journal of the American Chemical Society, vol. 72, pp. 12541263(1950).

CHARLES E. PARKER, Primary Examiner 10 S. T. LAWRENCE III, AssistantExaminer US. Cl. X.R.

